The present invention relates to phenylacetylene compounds having a phenylacetylene structure and an acryl or methacryl group on both ends of the structure via a spacer, which compounds are useful for preparing optical, display, and recording materials, and also for preparing optical compensators, polarizers, reflector plates, and scattering plates, which are used for liquid crystal devices, or films having coloring effect, or useful as a material for preparing the above products or as a component of liquid crystal materials used for preparing liquid crystal display elements. The present invention also relates to liquid crystal compositions, polymers, optically anisotropic products, all containing such phenylacetylene compounds, and liquid crystal or optical elements utilizing the above.
There have recently been discussed possible applications of liquid crystalline materials not only to a switching element of a display for switching the display modes such as TN or STN mode, but also to retarder plates, polarizing plates, polarizing prisms, beam splitters, reflectors, holographic elements, color separators, or various optical filters, which make use of the optical anisotropy of the materials such as alignment and refractive index. Improvement in performance of display elements has become essential with the recent development in information-oriented society.
As techniqued for realizing production of optically anisotropic products from liquid crystalline materials, there are known, for example, methods of photopolymerizing a liquid crystalline compound having a polymerizable functional group or a polymerizable liquid crystal composition containing such a compound, by irradiating the compound or the composition in a liquid crystal state with ultra-violet or visible irradiation. These methods intend to, in other words, to produce a polymer wherein the alignment of liquid crystal molecules in a liquid crystal state is semipermanently fixed for achieving stable optical functions. As such liquid crystalline compounds having a polymerizable functional group, JP-A-11 116 534 and JP-A-11 80 081 propose mainly a compound having a phenylbenzoate core and a compound having a core including phenylbenzoate, cyclohexylphenyl, and tolan. The core structures of these compounds, however, do not give a high refractive index anisotropy (xcex94n).
On the other hand, as liquid crystalline compounds having a relatively high refractive index anisotropy, JP-A-2 83 340 and JP-A-9 216 841 propose conjugate compounds. However, such conjugate compounds do not have a sufficiently high refractive index anisotropy, have problems such as low solubility in other liquid crystals, and do not have a photopolymerizability.
It is therefore an object of the present invention to provide novel phenylacetylene compounds, liquid crystal compositions containing such a compound, polymers obtained from such a composition, and optically anisotropic products, which are expected to exhibit high refractive index anisotropy, easy to mix with other liquid crystal compounds, and has advantageous stability against light, and which may be used for preparation of optical compensators, polarizer materials, reflectors, scattering plates, or films having coloring effect.
It is another object of the present invention to provide liquid crystal or optical elements useful for producing optical shutters, display elements, or the like devices, which utilizes a novel phenylacetylene compound, a liquid crystal composition containing such a compound, a polymer obtained from such a composition, and an optically anisotropic product, which are expected to exhibit high refractive index anisotropy, easy to mix with other liquid crystal compounds, and has advantageous stability against light, and which may be used for preparation of optical compensators, polarizer materials, reflectors, scattering plates, or films having coloring effect.
According to the present invention, there is provided a phenylacetylene compound represented by the formula (1): 
wherein A1 to A12 each independently stands for a hydrogen atom, a fluorine atom, or an alkyl or alkoxy group having 1 to 10 carbon atoms optionally substituted with at least one fluorine atom; B1 and B2 each stands for a hydrogen atom or a methyl group; p, q, r, s, and t each denotes 0 or 1, provided that when q is 0, at least one of A2 and A4 to A10 stands for an alkyl or alkoxy group having 1 to 10 carbon atoms optionally substituted with at least one fluorine atom; m and n each denotes an integer of 0 to 14, provided that when s is 1, n is not 0, and when t is 1, m is not 0; W stands for a single bond, xe2x80x94CH2CH2xe2x80x94, or xe2x80x94Cxe2x89xa1Cxe2x80x94.
According to the present invention, there is also provided a liquid crystal composition comprising a phenylacetylene compound represented by the above formula (1).
According to the present invention, there is also provided a polymer obtained by polymerization of the above liquid crystal composition.
According to the present invention, there is further provided an optically anisotropic product produced using the above polymer.
According to the present invention, there is further provided a liquid crystal or optical element produced using at least one material selected from the group consisting of the phenylacetylene compound, the liquid crystal composition, the polymer, the optically anisotropic product.
Phenylacetylene compounds of the present invention are represented by the formula (1) In the formula (1) A1 to A12 each independently stands for a hydrogen atom, a fluorine atom, or an alkyl or alkoxy group having 1 to 10 carbon atoms optionally substituted with at least one fluorine atom. B1 and B2 each stands for a hydrogen atom or a methyl group. p, q, r, s, and t each denotes 0 or 1, provided that when q is 0, at least one of A2 and A4 to A10 stands for an alkyl or alkoxy group having 1 to 10 carbon atoms optionally substituted with at least one fluorine atom. m and n each denotes an integer of 0 to 14, provided that when s is 1, n is not 0, and when t is 1, m is not 0. W stands for a single bond, xe2x80x94CH2 CH2xe2x80x94, or xe2x80x94Cxe2x89xa1Cxe2x80x94.
Examples of the phenylacetylene compounds represented by the formula (1) may include those represented by the formulae below, wherein m and n each denotes an integer of 1 to 14. Particularly preferred are phenylacetylene compounds represented by the formula (1 ) wherein at least one of A4, A5, A9 and A10 stands for an alkyl or alkoxy group having 1 to 10 carbon atoms optionally substituted with at least one fluorine atom, or phenylacetylene compounds represented by the formula (1 ) wherein s and t both denote 1. 
The phenylacetylene compounds of the present invention may be synthesized through ordinary organic synthesizing processes, for example, in accordance with the synthesizing process mentioned below, which is a combination of known unit processes.
Compounds represented by the formula (1) wherein (p, q, r, s, t)=(0, 0, 0, 0, 0), referred to as compound (1aa) hereinbelow, may be produced, for example, according to the following synthesizing process. 
In the formulae above, A2, A4 to A10, B1, B2, m, and n mean the same as in the formula (1). X1, X2, and X6 to X8 each independently stands for a halogen atom, and X3 to X5 each independently stands for a halogen atom, xe2x80x94OSO2CF3, or xe2x80x94OSO2C4F9. Y1 stands for xe2x80x94CF3 or xe2x80x94C4 F9, and P1 to P3 each independently stands for a protecting group for a hydroxyl group.
The reaction for preparing the compound represented by the formula (7) from the compound represented by the formula (6) in the above example of synthesis may be effected, for example, through the following Method (A1) or (B1):
Method (A1): Reacting the compound represented by the formula (6) with 1,1-dimethyl-2-propynol in the presence of copper iodide, a palladium catalyst, or a base such as triethylamine, followed by reaction with a base such as an alkali hydroxide;
Method (B1): Reacting the compound represented by the formula (6) with trimethylsilylacetylene in the presence of copper iodide, a palladium catalyst, or a base such as triethylamine, followed by reaction with a base such as an alkali carbonate.
The coupling reaction of the compounds represented by the formulae (7) and (8) in the above example of synthesis may be effected by reaction of the two compounds in the presence of copper iodide, a palladium catalyst, or a base such as triethylamine.
Compounds represented by the formula (1) wherein (p, q, r, s, t)=(0, 0, 1, 0, 0), referred to as compound (1ab) hereinbelow, may be produced, for example, according to the following synthesizing process. 
In the formulae above, A2, A4 to A10, B1, B2, m, and n mean the same as in the formula (1). X7 and X8 each independently stands for a halogen atom, and X4 stands for a halogen atom, xe2x80x94OSO2CF3, or xe2x80x94OSO2C4F9. P2 and P3 each independently stands for a protecting group for a hydroxyl group.
The coupling reaction of the compounds represented by the formulae (9) and (15) in the above example of synthesis may be effected by reaction of the two compounds in the presence of copper iodide, a palladium catalyst, or a base such as triethylamine.
Compounds represented by the formula (1) wherein (p, q, r, s, t)=(0, 1, 0, 0, 0) referred to as compound (1ac) hereinbelow, may be produced, for example, according to the following synthesizing process. 
In the formulae above, A1 to A12, B1, B2, W, m, and n mean the same as in the formula (1). X7 to X10 each independently stands for a halogen atom, and X4 stands for a halogen atom, xe2x80x94OSO2CF3, or xe2x80x94OSO2C4F9. P2 and P3 each independently stands for a protecting group for a hydroxyl group. Q stands for B(OZ1)2 or SnZ23, wherein Z1 stands for a hydrogen atom or an alkyl group, two Z1""s may be bonded to form a ring, and Z2 stands for an alkyl group or a halogen atom.
The coupling reaction of the compounds represented by the formulae (9) and (19) may be effected by reaction of the two compounds in the presence of a palladium catalyst or a base such as sodium carbonate.
Compounds represented by the formula (1) wherein (p, q, r, s, t)=(0, 1, 1, 0, 0), referred to as compound (1ad) hereinbelow, may be produced, for example, according to the following synthesizing process. 
In the formulae above, A1 to A2, B1, B2, W, m, and n mean the same as in the formula (1). X7, X8, X10, and X11 each independently stands for a halogen atom, and X3 and X4 each independently stands for a halogen atom, xe2x80x94OSO2CF3, or xe2x80x94OSO2C4 F9. Y1 stands for xe2x80x94CF3 or xe2x80x94C4F9, and P2 to P4 each independently stands for a protecting group for a hydroxyl group.
The reaction for preparing the compound represented by the formula (24) from the compound represented by the formula (23) in the above example of synthesis may be effected, for example, through the following Method (A2) or (B2):
Method (A2): Reacting the compound represented by the formula (23) with 1,1-dimethyl-2-propynol in the presence of copper iodide, a palladium catalyst, or a base such as triethylamine, followed by reaction with a base such as an alkali hydroxide;
Method (B2): Reacting the compound represented by the formula (23) with trimethylsilylacetylene in the presence of copper iodide, a palladium catalyst, or a base such as triethylamine, followed by reaction with a base such as an alkali carbonate.
The coupling reaction of the compounds represented by the formulae (9) and (24) in the above example of synthesis may be effected by reaction of the two compounds in the presence of copper iodide, a palladium catalyst, or a base such as triethylamine.
Compounds represented by the formula (1) wherein (p, q, r, s, t)=(1, 0, 0, 0, 0), referred to as compound (1ae) hereinbelow, may be produced, for example, according to the following synthesizing process. 
In the formulae above, A2, A4 to A10, B1, B2, m, and n mean the same as in the formula (1). X7, X8, and X12 each independently stands for a halogen atom, and X4 stands for a halogen atom, xe2x80x94OSO2CF3, or xe2x80x94OSO2C4F9. P2 and P3 each independently stands for a protecting group for a hydroxyl group.
Compounds represented by the formula (1) wherein (p, q, r, s, t)=(1, 0, 1, 0, 0), referred to as compound (1af) hereinbelow, may be produced, for example, according to the following synthesizing process. 
In the formulae above, A2, A4 to A10, B1, B2, m, and n mean the same as in the formula (1). X7 and X8 each independently stands for a halogen atom, and X4 stands for a halogen atom, xe2x80x94OSO2CF3, or xe2x80x94OSO2C4F9. P2 and P3 each independently stands for a protecting group for a hydroxyl group.
The coupling reaction of the compounds represented by the formulae (9) and (28) in the above example of synthesis may be effected by reaction of the two compounds in the presence of copper iodide, a palladium catalyst, or a base such as triethylamine.
Compounds represented by the formula (1) wherein (p, q, r, s, t)=(1, 1, 0, 0, 0) referred to as compound (1ag) hereinbelow, may be produced, for example, according to the following synthesizing process. 
In the formulae above, A1 to A12, B1, B2, W, m, and n mean the same as in the formula (1). X7 to X9 and X13 each independently stands for a halogen atom, and X4 stands for a halogen atom, xe2x80x94OSO2CF3, or xe2x80x94OSO2C4F9. P2 and P3 each independently stands for a protecting group for a hydroxyl group. Q stands for B(OZ1)2 or SnZ23, wherein Z1 stands for a hydrogen atom or an alkyl group, two Z1""s may be bonded to form a ring, and Z2 stands for an alkyl group or a halogen atom.
The coupling reaction of the compounds represented by the formulae (9) and (31) may be effected by reaction of the two compounds in the presence of a palladium catalyst or a base such as sodium carbonate.
Compounds represented by the formula (1) wherein (p, q, r, s, t)=(1, 1, 1, 0, 0) referred to as compound (1ah) hereinbelow, may be produced, for example, according to the following synthesizing process. 
In the formulae above, A1 to A12, B1, B2, W, m, and n mean the same as in the formula (1). X7, X8, X11, and X13 each independently stands for a halogen atom, and X3 and X4 each independently stands for a halogen atom, xe2x80x94OSO2CF3, or xe2x80x94OSO2C4F9. Y1 stands for xe2x80x94CF3 or xe2x80x94C4F9, and P2 to P4 each independently stands for a protecting group for a hydroxyl group.
The reaction for preparing the compound represented by the formula (36) from the compound represented by the formula (35) in the above example of synthesis may be effected, for example, through the following Method (A3) or (B3):
Method (A3): Reacting the compound represented by the formula (35) with 1,1-dimethyl-2-propynol in the presence of copper iodide, a palladium catalyst, or a base such as triethylamine, followed by reaction with a base such as an alkali hydroxide;
Method (B3) :Reacting the compound represented by the formula (35) with trimethylsilylacetylene in the presence of copper iodide, a palladium catalyst, or a base such as triethylamine, followed by reaction with a base such as an alkali carbonate.
The coupling reaction of the compounds represented by the formulae (9) and (36) in the above example of synthesis may be effected by reaction of the two compounds in the presence of copper iodide, a palladium catalyst, or a base such as triethylamine.
Compounds represented by the formula (1) wherein (p, q, r, s, t)=(0, 0, 0, 1, 1), referred to as compound (1 ba) hereinbelow, may be produced, for example, according to the following synthesizing process. 
In the formulae above, A2, A4 to A10, B1, B2, m, and n mean the same as in the formula (1). X2 and X6 to X8 each independently stands for a halogen atom, and X12 stands for a halogen atom, xe2x80x94OSO2CF3, or xe2x80x94OSO2C4F9. P2 and P4 each independently stands for a protecting group for a hydroxyl group.
The coupling reaction of the compounds represented by the formulae (39) and (40) in the above example of synthesis may be effected by reaction of the two compounds in the presence of copper iodide, a palladium catalyst, or a base such as triethylamine.
Compounds represented by the formula (1) wherein (p, q, r, s, t)=(0, 0, 1, 1, 1) referred to as compound (1bb) hereinbelow, may be produced, for example, according to the following synthesizing process. 
In the formulae above, A2, A4 to A10, B1, B2, m, and n mean the same as in the formula (1). X5, X7, and X8 each independently stands for a halogen atom, and X4 and X12 each independently stands for a halogen atom, xe2x80x94OSO2CF3, or xe2x80x94OSO2C4F9. R1 stands for an alkyl group having 1 to 4 carbon atoms or a phenyl group, and P2 and P3 each independently stands for a protecting group for a hydroxyl group.
The reaction for preparing the compound represented by the formula (43) from the compound represented by the formula (39) in the above example of synthesis may be effected, for example, through the following Method (A4) or (B4):
Method (A4): Reacting the compound represented by the formula (39) with 1,1-dimethyl-2-propynol in the presence of copper iodide, a palladium catalyst, or a base such as triethylamine, followed by reaction with a base such as an alkali hydroxide;
Method (B4): Reacting the compound represented by the formula (39) with trimethylsilylacetylene in the presence of copper iodide, a palladium catalyst, or a base such as triethylamine, followed by reaction with a base such as an alkali carbonate.
The coupling reaction of the compounds represented by the formulae (8) and (43) in the above example of synthesis may be effected by reaction of the two compounds in the presence of copper iodide, a palladium catalyst, or a base such as triethylamine.
The coupling reaction of the compounds represented by the formulae (44) and (45) in the above example of synthesis may be effected by reaction of the two compounds in the presence of a palladium catalyst.
Compounds represented by the formula (1) wherein (p, q, r, s, t)=(0, 1, 0, 1, 1), referred to as compound (1bc) hereinbelow, may be produced, for example, according to the following synthesizing process. 
In the formulae above, A1 to A12, B1, B2, W, m, and n mean the same as in the formula (1). X7 to X9 and X14 each independently stands for a halogen atom, and X4 stands for a halogen atom, xe2x80x94OSO2CF3, or xe2x80x94OSO2C4F9. P2 and P3 each independently stands for a protecting group for a hydroxyl group. Q stands for B(OZ1)2 or SnZ23, wherein Z1 stands for a hydrogen atom or an alkyl group, two Z1""s may be bonded to form a ring, and Z2 stands for an alkyl group or a halogen atom.
The coupling reaction of the compounds represented by the formulae (44) and (48) maybe effected by reaction of the two compounds in the presence of a palladium catalyst or a base such as sodium carbonate.
Compounds represented by the formula (1) wherein (p, q, r, s, t)=(0, 1, 1, 1, 1), referred to as compound (1bd) hereinbelow, may be produced, for example, according to the following synthesizing process. 
In the formulae above, A1 to A12, B1, B2, W, m, and n mean the same as in the formula (1). X7, X8, X11, and X15 each independently stands for a halogen atom, and X3 and X4 each independently stands for a halogen atom, xe2x80x94OSO2CF3, or xe2x80x94OSO2C4F9. P2 to P4 each independently stands for a protecting group for a hydroxyl group.
The reaction for preparing the compound represented by the formula (53) from the compound represented by the formula (52) in the above example of synthesis may be effected, for example, through the following Method (A5) or (B5):
Method (A5): Reacting the compound represented by the formula (52) with 1,1-dimethyl-2-propynol in the presence of copper iodide, a palladium catalyst, or a base such as triethylamine, followed by reaction with a base such as an alkali hydroxide;
Method (B5): Reacting the compound represented by the formula (52) with trimethylsilylacetylene in the presence of copper iodide, a palladium catalyst, or a base such as triethylamine, followed by reaction with a base such as an alkali carbonate.
The coupling reaction of the compounds represented by the formulae (44) and (53) in the above example of synthesis may be effected by reaction of the two compounds in the presence of copper iodide, a palladium catalyst, or a base such as triethylamine.
Compounds represented by the formula (1) wherein (p, q, r, s, t)=(1, 0, 0, 1, 1), referred to as compound (1be) hereinbelow, may be produced, for example, according to the following synthesizing process. 
In the formulae above, A2, A4 to A10, B1, B2, m, and n mean the same as in the formula (1). X4, X7, X8, and X16 each independently stands for a halogen atom. P2 and P3 each independently stands for a protecting group for a hydroxyl group.
Compounds represented by the formula (1) wherein (p, q, r, s, t)=(1, 0, 1, 1, 1), referred to as compound (1bf) hereinbelow, may be produced, for example, according to the following synthesizing process. 
In the formulae above, A2, A4 to A10, B1, B2, m, and n mean the same as in the formula (1). X7 and X8 each independently stands for a halogen atom, and X4 stands for a halogen atom, xe2x80x94OSO2CF3, or xe2x80x94OSO2C4F9. P2 and P3 each independently stands for a protecting group for a hydroxyl group.
The coupling reaction of the compounds represented by the formulae (44) and (57) in the above example of synthesis may be effected by reaction of the two compounds in the presence of copper iodide, a palladium catalyst, or a base such as triethylamine.
Compounds represented by the formula (1) wherein (p, q, r, s, t)=(1, 1, 0, 1, 1) referred to as compound (1bg) hereinbelow, may be produced, for example, according to the following synthesizing process. 
In the formulae above, A1 to A12, B1, B2, W, m, and n mean the same as in the formula (1). X7 to X9 and X17 each independently stands for a halogen atom, and X4 stands for a halogen atom, xe2x80x94OSO2CF3, or xe2x80x94OSO2C4F9. P2 and P3 each independently stands for a protecting group for a hydroxyl group. Q stands for B(OZ1)2 or SnZ23, wherein Z1 stands for a hydrogen atom or an alkyl group, two Z1""s may be bonded to form a ring, and Z2 stands for an alkyl group or a halogen atom.
The coupling reaction of the compounds represented by the formulae (44) and (60) maybe effected by reaction of the two compounds in the presence of a palladium catalyst or a base such as sodium carbonate.
Compounds represented by the formula (1) wherein (p, q, r, s, t)=(1, 1, 1, 1, 1), referred to as compound (1bh) hereinbelow, may be produced, for example, according to the following synthesizing process. 
In the formulae above, A1 to A12, B1, B2, W, m, and n mean the same as in the formula (1). X7, X8, X11, and X17 each independently stands for a halogen atom, and X3 and X4 each independently stands for a halogen atom, xe2x80x94OSO2CF3, or xe2x80x94OSO2C4F9. Y1 stands for xe2x80x94CF3 or xe2x80x94C4F9, and P2 to P4 each independently stands for a protecting group for a hydroxyl group.
The reaction for preparing the compound represented by the formula (64) from the compound represented by the formula (63) in the above example of synthesis may be effected, for example, through the following Method (A6) or (B6):
Method (A6): Reacting the compound represented by the formula (63) with 1,1-dimethyl-2-propynol in the presence of copper iodide, a palladium catalyst, or a base such as triethylamine, followed by reaction with a base such as an alkali hydroxide;
Method (B6): Reacting the compound represented by the formula (63) with trimethylsilylacetylene in the presence of copper iodide, a palladium catalyst, or a base such as triethylamine, followed by reaction with a base such as an alkali carbonate.
The coupling reaction of the compounds represented by the formulae (44) and (64) in the above example of synthesis may be effected by reaction of the two compounds in the presence of copper iodide, a palladium catalyst, or a base such as triethylamine.
Compounds represented by the formula (1) wherein (p, q, r, s, t)=(0, 0, 0, 0, 1), referred to as compound (1ca) hereinbelow, may be produced, for example, according to the same synthesizing process for the compound (1aa) except that the compound represented by the formula (6) is replaced with the compound represented by the formula (39).
Compounds represented by the formula (1) wherein (p, q, r, s, t)=(0, 0, 1, 0, 1), referred to as compound (1cb) hereinbelow, may be produced, for example, according to the same synthesizing process for the compound (1ab) except that the compound represented by the formula (9) is replaced with the compound represented by the formula (44).
Compounds represented by the formula (1) wherein (p, q, r, s, t)=(0, 1, 0, 0, 1), referred to as compound (1cc) hereinbelow, may be produced, for example, according to the same synthesizing process for the compound (1ac) except that the compound represented by the formula (9) is replaced with the compound represented by the formula (44).
Compounds represented by the formula (1) wherein (p, q, r, s, t)=(0, 1, 1, 0, 1), referred to as compound (1cd) hereinbelow, may be produced, for example, according to the same synthesizing process for the compound (1ad) except that the compound represented by the formula (9) is replaced with the compound represented by the formula (44).
Compounds represented by the formula (1) wherein (p, q, r, s, t)=(1, 0, 0, 0, 1), referred to as compound (1ce) hereinbelow, may be produced, for example, according to the same synthesizing process for the compound (1ae) except that the compound represented by the formula (9) is replaced with the compound represented by the formula (44).
Compounds represented by the formula (1) wherein (p, q, r, s, t)=(1, 0, 1, 0, 1), referred to as compound (1cf) hereinbelow, may be produced, for example, according to the same synthesizing process for the compound (1af) except that the compound represented by the formula (9) is replaced with the compound represented by the formula (44).
Compounds represented by the formula (1) wherein (p, q, r, s, t)=(1, 1, 0, 0, 1), referred to as compound (1cg) hereinbelow, may be produced, for example, according to the same synthesizing process for the compound (1ag) except that the compound represented by the formula (9) is replaced with the compound represented by the formula (44).
Compounds represented by the formula (1) wherein (p, q, r, s, t)=(1, 1, 1, 0, 1), referred to as compound (1ch) hereinbelow, may be produced, for example, according to the same synthesizing process for the compound (1ah) except that the compound represented by the formula (9) is replaced with the compound represented by the formula (44).
Compounds represented by the formula (1) wherein (p, q, r, s, t)=(0, 0, 0, 1, 0), referred to as compound (1da) hereinbelow, may be produced, for example, according to the following synthesizing process. 
In the formulae above, A2, A4 to A10, B1, B2, m, and n mean the same as in the formula (1). X6 to X8 each independently stands for a halogen atom, and X4 stands for a halogen atom, xe2x80x94OSO2CF3, or xe2x80x94OSO2C4F9. P2 to P4 each independently stands for a protecting group for a hydroxyl group.
The coupling reaction of the compounds represented by the formulae (7) and (66) in the above example of synthesis may be effected by reaction of the two compounds in the presence of copper iodide, a palladium catalyst, or a base such as triethylamine.
Compounds represented by the formula (1) wherein (p, q, r, s, t)=(0, 0, 1, 1, 0), referred to as compound (1db) hereinbelow, may be produced, for example, according to the same synthesizing process for the compound (1bb) except that the compound represented by the formula (44) is replaced with the compound represented by the formula (9).
Compounds represented by the formula (1) wherein (p, q, r, s, t)=(0, 1, 0, 1, 0), referred to as compound (1dc) hereinbelow, may be produced, for example, according to the same synthesizing process for the compound (1bc) except that the compound represented by the formula (44) is replaced with the compound represented by the formula (9).
Compounds represented by the formula (1) wherein (p, q, r, s, t)=(0, 1, 1, 1, 0), referred to as compound (1dd) hereinbelow, may be produced, for example, according to the same synthesizing process for the compound (1bd) except that the compound represented by the formula (44) is replaced with the compound represented by the formula (9).
Compounds represented by the formula (1) wherein (p, q, r, s, t)=(1, 0, 0, 1, 0), referred to as compound (1de) hereinbelow, may be produced, for example, according to the same synthesizing process for the compound (1be) except that the compound represented by the formula (44) is replaced with the compound represented by the formula (9).
Compounds represented by the formula (1) wherein (p, q, r, s, t)=(1, 0, 1, 1, 0), referred to as compound (1df) hereinbelow, may be produced, for example, according to the same synthesizing process for the compound (1bf) except that the compound represented by the formula (44) is replaced with the compound represented by the formula (9).
Compounds represented by the formula (1) wherein (p, q, r, s, t)=(1, 1, 0, 1, 0), referred to as compound (1dg) hereinbelow, may be produced, for example, according to the same synthesizing process for the compound (1bg) except that the compound represented by the formula (44) is replaced with the compound represented by the formula (9).
Compounds represented by the formula (1) wherein (p, q, r, s, t)=(1, 1, 1, 1, 0), referred to as compound (1dh) hereinbelow, may be produced, for example, according to the same synthesizing process for the compound (1bh) except that the compound represented by the formula (44) is replaced with the compound represented by the formula (9).
The liquid crystal compositions of the present invention contain one or more phenylacetylene compounds represented by the formula (1) above. The liquid crystal compositions may optionally contain other liquid crystalline materials depending on the purpose of the compounds, as long as their liquid crystal properties are maintained.
In the liquid crystal compositions of the present invention, the content of the one or more phenylacetylene compounds represented by the formula (1) may suitably be selected depending on the purpose of the compositions, but is usually not less than 50 wt %, preferably 60 to 90 wt % of the weight of the liquid crystal compositions.
Examples of such other liquid crystalline materials contained in the liquid crystal compositions of the present invention may preferably include liquid crystalline compounds represented by the formulae (xcex1-1) to (xcex1-3); monomer (A) having at least one kind of polymerizable functional group selected from the group consisting of a methacrylate ester, an acrylate ester, epoxy, and vinyl ether; or mixtures thereof: 
wherein A1 to A12 each independently stands for a hydrogen atom, a fluorine atom, an alkyl or alkoxy group having 1 to 10 carbon atoms optionally substituted with at least one fluorine atom; R1 and R2 each independently stands for a hydrogen atom, a fluorine atom, a cyano group, xe2x80x94SF5, xe2x80x94NCS, a 4-R3-(cycloalkyl) group, a 4-R3-(cycloalkenyl) group, or an R4xe2x80x94(O)q1 group, wherein R3 stands for a hydrogen atom or a straight or branched alkyl group having 1 to 12 carbon atoms optionally substituted with at least one fluorine atom, R4 stands for a straight or branched alkyl group having 1 to 12 carbon atoms optionally substituted with at least one fluorine atom, and q1 denotes 0 or 1; 
wherein A13 to A24 each independently stands for a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 10 carbon atoms; m is 0 or 1; R11 stands for a hydrogen atom or a straight or branched alkyl group having 1 to 12 carbon atoms optionally substituted with at least one fluorine atom; R21 stands for R11, a fluorine atom, a cyano group, a 4-R31-(cycloalkyl) group, a 4-R31-(cycloalkenyl) group, or an R41xe2x80x94(O) q2 group, wherein R31 stands for a hydrogen atom or a straight or branched alkyl group having 1 to 12 carbon atoms optionally substituted with at least one fluorine atom; R41 stands for an alkyl group having 1 to 12 carbon atoms optionally substituted with at least one fluorine atom; q2 is 0 or 1; 
wherein rings A, B, C, and D each independently stands for 1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclohexenylene, 4,1-cyclohexenylene, 2,5-cyclohexenylene, 5,2-cyclohexenylene, 3, 6-cyclohexenylene, 6,3-cyclohexenylene, 2,5-pyrimidinediyl, 5,2-pyrimidinediyl, 2,5-pyridinediyl, 5,2-pyridinediyl, 2,5-dioxanediyl, or 5,2-dioxanediyl, and at least one hydrogen atom on any of the rings A, B, C, and D may be substituted with a fluorine atom; R5 and R6 each independently stands for a hydrogen atom, a fluorine atom, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group, a cyano group, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyloxy group having 2 to 12 carbon atoms, an alkynyloxy group having 3 to 12 carbon atoms, an alkoxyalkyl group having 2 to 16 carbon atoms, or an alkoxyalkenyl group having 3 to 16 carbon atoms, wherein at least one methylene group of an alkyl, alkenyl, or alkynyl group may be replaced with an oxygen, sulfur, or silicon atom, and these groups may be straight or branched; Z1, Z2, and Z3 each independently stands for xe2x80x94COOxe2x80x94, xe2x80x94OCOxe2x80x94, xe2x80x94OCH2xe2x80x94, xe2x80x94CH2Oxe2x80x94, an alkylene group having 1 to 5 carbon atoms, an alkenylene group having 2 to 5 carbon atoms, an alkynylene group having 2 to 5 carbon atoms, or a single bond; b, c, and d each independently denotes 0 or 1 with b+c+dxe2x89xa71.
Examples of the compounds represented by the formula (xcex1-1) may include the compounds represented by the following formulae, which compounds may be synthesized through ordinary organic synthesizing processes: 
In the formula (xcex1-1), each of R1 and R2 may independently stands for, for example, a hydrogen atom; a fluorine atom; an alkyl group such as a methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl group, or an alkyl group substituted with at least one fluorine atom, i.e. a fluoroalkyl group such as a trifluoromethyl group; an alkoxy group such as a methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, or dodecyloxy group, or an alkoxy group substituted with at least one fluorine atom, i.e. a fluoroalkoxy group such as a methoxy group having 1 to 3 substituted fluorine atoms, or an ethoxy group having 1 to 5 substituted fluorine atoms; an alkoxyalkyl group such as a methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, pentyloxymethyl, hexyloxymethyl, heptyloxymethyl, octyloxymethyl, nonyloxymethyl, decyloxymethyl, methoxyethyl, ethoxyethyl, propoxyethyl, butoxyethyl, pentyloxyethyl, hexyloxyethyl, heptyloxyethyl, octyloxyethyl, nonyloxyethyl, decyloxyethyl, methoxypropyl, ethoxypropyl, propoxypropyl, butoxypropyl, pentyloxypropyl, hexyloxypropyl, heptyloxypropyl, octyloxypropyl, nonyloxypropyl, methoxybutyl, ethoxybutyl, propoxybutyl, butoxybutyl, pentyloxybutyl, hexyloxybutyl, heptyloxybutyl, octyloxybutyl, methoxypentyl, ethoxypentyl, propoxypentyl, butoxypentyl, pentyloxypentyl, hexyloxypentyl, or heptyloxypentyl, or an alkoxyalkyl group substituted with at least one fluorine atom, i.e., a fluoroalkoxyalkyl group; a branched alkyl group such as a 2-methylpropyl, 2-methylbutyl, 3-methylbutyl, or 3-methylpentyl group, or a branched alkyl group substituted with at least one fluorine atom, i.e., a branched fluoroalkyl group; a branched alkyloxy group such as a 2-methylpropyloxy, 2-methylbutyloxy, 3-methylbutyloxy, or 3-methylpentyloxy group, or a branched alkyloxy group substituted with at least one fluorine atom, i.e., a branched fluoroalkyloxy group; a 4-alkyl-cycloalkyl group such as a 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-propylcyclohexyl, 4-butylcyclohexyl, 4-pentylcyclohexyl, 4-hexylcyclohexyl, 4-heptylcyclohexyl, 4-octylcyclohexyl, 4-nonylcyclohexyl, or 4-decylcyclohexyl group, or a 4-alkyl-cycloalkyl group substituted with at least one fluorine atom, i.e., a 4-fluoroalkyl-cycloalkyl group; a 4-alkyl-cycloalkenyl group such as a 4-propylcyclohexenyl or 4-pentylcyclohexenyl group, or a 4-alkyl-cycloalkenyl group substituted with at least one fluorine atom, i.e., a 4-fluoroalkyl-cycloalkenyl group; a cyano group; xe2x80x94SF5; or xe2x80x94NCS.
Examples of the compounds represented by the formula (xcex1-2) may include the compounds represented by the following formulae, which compounds may be synthesized through ordinary organic synthesizing processes: 
In the formula (xcex1-2), examples of R11 and R21 may preferably include those listed above as examples of R1 and R2 in the formula (xcex1-1) and corresponding to R11 and R21, respectively.
Examples of the compounds represented by the formula (xcex1-3) may include the compounds represented by the following formulae. 
In the formulae, W stands for a hydrogen or fluorine atom; x denotes an integer of 0 to 3; ring H stands for 1,4-cyclohexylene; ring G stands for 1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclohexenylene, 4,1-cyclohexenylene, 2,5-cyclohexenylene, 5,2-cyclohexenylene, 3,6-cyclohexenylene, 6,3-cyclohexenylene, 2,5-pyrimidinediyl, 5,2-pyrimidinediyl, 2,5-pyridinediyl, 5,2-pyridinediyl, 2,5-dioxanediyl, or 5,2-dioxanediyl, all of which may optionally be substituted with at least one fluorine atom. The ring G preferably stands for 1,4-cyclohexylene, 1,4-cyclohexenylene, 4,1-cyclohexenylene, 2,5-cyclohexenylene, 5,2-cyclohexenylene, 3,6-cyclohexenylene, or 6,3-cyclohexenylene. Examples of R5 and R6 may include a hydrogen atom; a fluorine atom; a fluoromethyl group; a difluoromethyl group; a trifluoromethyl group; a fluoromethoxy group; a difluoromethoxy group; a trifluoromethoxy group; a cyano group; alkyl groups, such as a methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl group; alkenyl groups, such as an ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, or dodecenyl group; alkoxy groups, such as a methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, or dodecyloxy group; alkenyloxy group, such as a vinyl oxy, propenyloxy, butenyloxy, pentenyloxy, hexenyloxy, heptenyloxy, octenyloxy, nonenyloxy, or decenyloxy group; alkynyloxy groups, such as a propynyloxy, butynyloxy, pentynyloxy, hexynyloxy, heptynyloxy, octynyloxy, nonynyloxy, decynyloxy, undecynyloxy, or dodecynyloxy group; alkoxyalkyl groups, such as a methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, pentyloxymethyl, hexyloxymethyl, heptyloxymethyl, octyloxymethyl, nonyloxymethyl, decyloxymethyl, methoxyethyl, ethoxyethyl, propoxyethyl, butoxyethyl, pentyloxyethyl, hexyloxyethyl, heptyloxyethyl, octyloxyethyl, nonyloxyethyl, decyloxyethyl, methoxypropyl, ethoxypropyl, propoxypropyl, butoxypropyl, pentyloxypropyl, hexyloxypropyl, heptyloxypropyl, octyloxypropyl, nonyloxypropyl, decyloxypropyl, methoxybutyl, ethoxybutyl, propoxybutyl, butoxybutyl, pentyloxybutyl, hexyloxybutyl, heptyloxybutyl, octyloxybutyl, nonyloxybutyl, decyloxybutyl, methoxypentyl, ethoxypentyl, propoxypentyl, butoxypentyl, pentyloxypentyl, hexyloxypentyl, heptyloxypentyl, octyloxypentyl, nonyloxypentyl, or decyloxypentyl group.
These compounds may be synthesized through ordinary organic synthesizing processes.
Examples of the monomer (A) may include the compounds represented by the formula (xcex2), which may be synthesized through ordinary organic synthesizing processes: 
wherein rings A, B, C, and D, Z1, Z2, Z3, b, c, and d mean the same as in the formula (xcex1-3); R7 and R8 each independently stands for an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkoxyalkyl group having 2 to 16 carbon atoms, wherein at least one methylene group of an alkyl group may be replaced with an oxygen, sulfur, or silicon atom, and these groups may be straight or branched; P1 and P2 each stands for a methacrylate ester, an acrylate ester, epoxy, vinyl ether, a hydrogen atom, a fluorine atom, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group, or a cyano group, provided that at least one of P1 and P2 stands for a methacrylate ester, an acrylate ester, epoxy, or vinyl ether; e and f each denotes 0 or 1, provided that not both of e and f denote 0.
Examples of the compounds represented by the formula (xcex2) may include the compounds represented by the following formulae: 
wherein A stands for a hydrogen atom, a fluorine atom, or a methyl group; A1 and A2 each stands for a hydrogen or fluorine atom; X and Y each independently stands for a group selected from the following groups, provided that not both X and Y simultaneously denote xe2x80x94(O)hxe2x80x94(CH2)ixe2x80x94CH3: 
wherein e and h each denotes 0 or 1; f and i each denotes an integer of 1 to 12; Z1 stands for a hydrogen atom or a methyl group.
The content of other liquid crystalline compounds mentioned above, when contained, may suitably be decided depending on the purpose of the liquid crystal compositions, but is usually selected from the range of 10 to 50 wt %, preferably 10 to 40 wt % of the liquid crystal compositions.
The liquid crystal compositions of the present invention may optionally contain a chiral (optically active) compound, which does not necessarily exhibit liquid crystal properties itself. Examples of the chiral compound may include the following compounds, and the content of the chiral compound may suitably be decided: 
When the liquid crystal compositions of the present invention are used for preparing, for example, polarizing films, printing inks, or paints, the compositions may optionally contain pigments, coloring agents, or dyes in a suitable amount, depending on the purpose of the liquid crystal compositions.
The polymers of the present invention have been obtained by polymerizing liquid crystal compositions containing one or more phenylacetylene compounds represented by the formula (1), which compositions may optionally contain other materials such as other liquid crystalline materials exemplified above.
When compounds not having a photopolymerizable functional group are used as such other materials, the content of such compounds may be decided depending on the purpose, as long as liquid crystal properties are not impaired. However, where the temperature-dependent change in the refractive index anisotropy is not desired, the content of such compounds is preferably in the range of 0 to 50 wt % of all the monomers contained in the liquid crystal compositions.
As other materials mentioned above, compounds that have at least one photopolymerizable functional group and not exhibit liquid crystal properties may also be used. Any compounds recognized in the art as polymerizable monomers or oligomers may be used as such compounds, and acrylate compounds, methacrylate compounds, and vinyl ether compounds are particularly preferred.
In the liquid crystal compositions for producing the polymers of the present invention, the ratio of the one or more phenylacetylene compounds represented by the formula (1) and the other materials may suitably be decided depending on the purpose of the polymers, but it is usually preferred to select the ratio from the range of 90:10 to 50:50 by weight.
The liquid crystal compositions for producing the polymers of the present invention may also contain a chiral (optically active) compound for the purpose of producing twisted oriented polymers. In this case, the chiral compound itself does not necessarily exhibit liquid crystal properties, and does not necessarily have a polymerizable functional group. Examples of the chiral compound may include those listed above. The content of the chiral compound may suitably be decided depending on the purpose of the polymers.
The molecular weight and other characteristics of the polymers of the present invention are not particularly limited, and polymers obtained under the following polymerization conditions are preferred.
Preferred methods for producing the polymers of the present invention include photopolymerization by irradiation with energy beams such as ultraviolet rays or electron beams. A light source for effecting such photopolymerization may be those emitting polarized light or those emitting unpolarized light. When a polymerization initiator that absorbs light of the visible region is added to the liquid crystal material, irradiation may be performed with visible light. In this case, two laser beams may be caused to interfere with the visible light to thereby give spatially distributed intensity to the light beams. The irradiation temperature is preferably in the range for allowing maintenance of the liquid crystal state of the liquid crystal compositions of the present invention. When an optically anisotropic product is to be produced by photopolymerization, it is particularly preferred to polymerize the liquid crystal compositions at a temperature as close to the room temperature as possible in order to avoid induction of unintended thermal polymerization. The optically anisotropic product obtained by the polymerization may further be subjected to a heat treatment for inhibiting change in its initial characteristics to steadily maintain the characteristics. The heat treatment may preferably be carried out at a temperature in the range of approximately 50 to 200xc2x0 C. for a period in the range of 30 seconds to 12 hours.
In order to improve the polymerizability, a thermal polymerization initiator or a photopolymerization initiator may be added to the liquid crystal compositions. Examples of the thermal polymerization initiator may include benzoyl peroxide and bisazobutylonitrile, and examples of the photopolymerization initiator may include benzoin ethers, benzophenones, acetophenones, and benzylketals.
The amount of the polymerization initiator is preferably not more than 10 wt %, more preferably 0.5 to 1.5 wt % of the total weight of the monomers to be polymerized.
The optically anisotropic products of the present invention have been produced using the polymers of the present invention discussed above.
An optically anisotropic product of the present invention may be produced, for example, by preparing a liquid crystal composition for producing a polymer of the present invention so that the composition exhibits liquid crystal properties, and polymerizing the composition with liquid crystal molecules being aligned. More specifically, the optically anisotropic product may be produced by polymerizing the liquid crystal composition carried on a substrate or held between substrates. The substrate used here may have an organic thin film, for example, of polyimide, formed on its surface. The surface of the substrate may either be rubbed with a cloth or has an alignment layer formed by obliquely evaporating SiO2. It is convenient and preferred to use a substrate with an organic thin film formed thereon that has been rubbed with a cloth. The substrate may be made of either an organic or inorganic material.
Examples of the organic material for the substrate may include polycarbonate, polyethylene terephthalate, polystyrene, polyvinyl chloride, polyalylate, triacetyl cellulose, and polysulfone. Examples of the inorganic material for the substrate may include glass and silicone.
When the alignment of the liquid crystal molecules is controlled by an electric field, a substrate having an electrode layer may be used, on which layer the polyimide thin film is preferably formed. For alignment of the liquid crystal molecules, photo-alignment technique may also be used instead of the rubbing method. Alternatively, it is also possible to align the liquid crystal molecules by drawing following the polymerization of the liquid crystal composition.
In producing the optically anisotropic products of the present invention, conditions for the polymerization may suitably be selected from those for producing the polymers of the present invention discussed above. For example, the polymerization may include photopolymerization by irradiation with energy beams such as ultraviolet rays or electron beams. A light source for the photopolymerization may either be a source of polarized light or unpolarized light. The temperature of the irradiation may be decided depending on the purpose and may suitably be selected, since it is sometimes preferred to effect the polymerization in a temperature range wherein the liquid crystal state of the liquid crystal composition is maintained, or in some other times, it is preferred to effect the polymerization in a temperature range wherein the composition is in an isotropic phase.
The optically anisotropic products of the present invention obtained through the processes discussed above may be used as they are with the substrate, or only the polymer layer may be peeled off for use as the optically anisotropic product.
The liquid crystal or optical elements of the present invention include any element that has been produced using a phenylacetylene compound of the present invention, a liquid crystal composition containing the compound, a polymer obtained by polymerizing the composition, or an optically anisotropic product produced using the polymer. These materials may be used, for example, for preparing optical, display, or recording materials, or for preparing optical compensators, polarizers, reflectors, scattering plates, films having coloring effect, or liquid crystal materials. Other constructions of the liquid crystal or optical elements are not particularly limited, and may suitably be selected according to the known methods and depending on the purpose.